The Metal-Metal-to-Ligand Charge Transfer Excited State and Supramolecular Polymerization of Luminescent Pincer PdII -Isocyanide Complexes.

ABSTRACT

Pincer PdII -isocyanide complexes are described that display intermolecular interactions and emissive 3 MMLCT excited states in aggregation state(s) at room temperature. The intermolecular PdII -PdII and ligand-ligand interactions drive these complexes to undergo supramolecular polymerization in a living manner. Comprehensive spectroscopic studies reveal a pathway with a kinetic trap that can be modulated by changing the counteranion and metal atom. The PdII supramolecular assemblies comprise two different aggregation forms with only one to be emissive. DFT/TDDFT calculations lend support to the MMLCT absorption and emission of these pincer PdII -isocyanide aggregates.